DEVELOPMENT OF NEW CHEMISTRY FOR A DUAL USE HYDRAZINE THRUSTER SWITCHABLE ROOM TEMPERATURE IONIC LIQUIDS A STUDY OF SILANE GRAFTING TO MODEL POLYETHYLENE COMPOUNDS SYNTHESIS OF THE NOVEL HYDRAZINE REPLACEMENT FUEL MOLECULES 1,1-DIMETHYL-2-[2-AZIDOETHYL]HYDRAZINE AND 1,1- DIMETHYL-2-[2-AZIDOETHYL]HYDRAZONE A Dissertation Presented to The Academic Faculty By Hillary Anne Huttenhower In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy in Chemistry Georgia Institute of Technology August, 2010 DEVELOPMENT OF NEW CHEMISTRY FOR A DUAL USE HYDRAZINE THRUSTER SWITCHABLE ROOM TEMPERATURE IONIC LIQUIDS A STUDY OF SILANE GRAFTING TO MODEL POLYETHYLENE COMPOUNDS SYNTHESIS OF THE NOVEL HYDRAZINE REPLACEMENT FUEL MOLECULES 1,1-DIMETHYL-2-[2-AZIDOETHYL]HYDRAZINE AND 1,1- DIMETHYL-2-[2-AZIDOETHYL]HYDRAZONE Dr. Charles L. Liotta, Advisor Dr. Charles A. Eckert School of Chemistry and Biochemistry School of Chemical and Biomolecular Georgia Institute of Technology Engineering Georgia Institute of Technology Dr. David M. Collard Dr. Rigoberto Hernandez School of Chemistry and Biochemistry School of Chemistry and Biochemistry Georgia Institute of Technology Georgia Institute of Technology Dr. Amyn Teja Date Approved: April 6, 2010 School of Chemical and Biomolecular Engineering Georgia Institute of Technology For Mom, Dad, and John- Who all believed in me even when I didn’t believe in myself ACKNOWLEDGEMENTS First and foremost, I would like to thank my advisor, Dr. Charles Liotta. I came to Georgia Tech specifically to work in his research group, and I have never once been disappointed. I would also like to thank my co-advisor, Dr. Charles Eckert. I have learned so much from both of these two researchers. Before I began graduate school, I never could have imagined the opportunities and experiences that awaited me here, and so many of them were thanks to the fact that I had these two gentlemen on my side. I would also like to thank the researchers at American Pacific that I have been fortunate enough to work with over the years. Some of the most interesting experiences that I have had have come out of collaboration with this company. Next, I would like to thank my committee. Everyone in academia is busy all the time, so I appreciate you finding time in your schedules to read my work and advise me during my time here. I would also like to thank every single member of the Eckert-Liotta group, past and present that I have worked with over the years. Ours truly is a collaborative group, and I couldn’t have done this without any of you. There are a few members in particular over the years that I couldn’t have gotten by without. Ejae John, my first mentor in lab, Stuart Terrett, the best undergrad anyone could ask for, Kristen Kitagawa, my office mate and fellow traveler on this crazy journey for so many years, Pamela Pollet, who keeps us all on track, thank you to all of you. A lot of the analysis necessary for this thesis could not be performed in house, so I would like to acknowledge all who helped with that. Thank you to Jung-il Hong for performing all the XRD analysis, Jeannette Taylor and Art McCanna at the Robert P. Apkarian Integrated Electron Microscopy Core facility at Emory University for iv performing TEM and SEM imaging, Oguz Karvan and the other members of the Koros group for the BET analysis, and the workers at Columbia Analytical Services for running all metals analysis and expediting them for free when I asked. I also need to thank my friends and especially my family. I hope my parents know how truly grateful I am, from the bottom of my heart, for all that they have done for me over the past five years of graduate school. I never ever would have made it through or even stayed sane without their love and support. It means so much to know that I can always count on them. Also, to my friend, Sara Campbell, though we were at different universities, we went through this crazy chemistry graduate school journey together, and it so helped to have someone to commiserate with. Though some may find this unusual, I also need to thank my cat, Winston, for all the moral support he’s given me over these years. At this point, I think he knows as much about this research as I do, since his favorite place while I was writing this dissertation was curled up around my computer. Finally, to my long-time boyfriend John, you have been a best friend, a source of comfort, a reminder that there is far more to life than work. We both know it’s been a bumpy road, but I’m glad we went through it together. When I actually take the time to step back and realize it, I know that I am truly blessed in so many ways, and I just want to thank God and everyone else who makes that possible. v TABLE OF CONTENTS ACKNOWLEDGEMENTS………………………………………………………. iv LIST OF TABLES………………………………………………………………... x LIST OF FIGURES………………………………………………………………. xii LIST OF SYMBOLS AND ABBREVIATIONS………………………………… xxv SUMMARY………………………………………………………………………. xxvii CHAPTER 1. INTRODUCTION………………………………………………… 1 1.1 References…………………………………………………………… 4 CHAPTER 2. DEVELOPMENT OF NEW CHEMISTRY FOR A DUAL USE HYDRAZINE THRUSTER……………………………………………………… 6 2.1 Introduction………………………………………………………….. 6 2.2 Background………………………………………………………….. 8 2.2.1 Hydrazine Decomposition……………………………………… 8 2.2.2 Catalyst Synthesis……………………………………………… 9 2.2.3 Liquid Chemical Propulsion…………………………………… 12 2.2.4 Electric Propulsion……………………………………………... 12 2.2.5 Benefits of a Dual Propulsion System………………………..... 15 2.3 Results and Discussion……………………………………………..... 16 2.3.1 Catalyst Synthesis……………………………………………… 16 2.3.1.1 Nanoparticle Synthesis…………………………………..... 16 2.3.1.2 Supported Nanoparticle Synthesis………………………... 32 2.3.1.3 Supported Catalyst Synthesis by the Shell Method……..... 43 2.3.1.4 Comparison of Supported Nanoparticle and Shell Synthesis Methods………………………………………... 49 2.3.2 Hydrazine Safety……………………………………………….. 49 2.3.3 Hydrazine Reactor and Analysis Design……………………..... 51 2.3.4 Analysis of Product Gas Stream……………………………….. 55 2.3.5 GC-TCD Analysis Modifications……………………………… 58 2.3.6 Decomposition of Hydrazine – First Generation Reactor……… 62 2.3.7 Decomposition of Hydrazine – Second Generation Reactor…... 67 2.4 Conclusions.......................................................................................... 69 2.5 Experimental........................................................................................ 71 2.6 References............................................................................................ 97 CHAPTER 3. SWITCHABLE ROOM TEMPERATURE IONIC LIQUIDS…… 102 vi 3.1 Introduction.......................................................................................... 102 3.2 Background.......................................................................................... 103 3.2.1 Room Temperature Ionic Liquids................................................ 103 3.2.2 Reversible Ionic Liquids……………………………………..… 104 3.2.3 Two Component Ionic Liquids………………………………… 105 3.2.3.1 Guanidine Based Ionic Liquids…………………………… 105 3.2.4 One Component Ionic Liquids………………………………..... 108 3.3 Results and Discussion……………………………………………..... 109 3.3.1 Two Component Ionic Liquids………………………………… 109 3.3.1.1 Synthesis of 2-butyl-1,1,3,3-tetramethylguanidine (TMBG)…………………………………………………... 109 3.3.1.2 Alternative Approach for the Synthesis of 2-butyl- 1,1,3,3-tetramethylguanidine……………………………... 112 3.3.1.3 Synthesis and Characterization of the Ionic Liquid 2- butyl-1,1,3,3-tetramethylguanidinium methylcarbonate….. 116 3.3.1.4 Relative Polarities of Various Solvents with 2-butyl- 1,1,3,3-tetramethylguanidinium alkylcarbonates ……….... 118 3.3.1.5 Structure Property Relationships in all Synthesized 2 -butyl-1,1,3,3-tetramethylguanidinium alkylcarbonates….. 122 3.3.1.6 Reversibility of 2-butyl-1,1,3,3-tetramethylguanidinium methylcarbonate…………………………………………... 123 3.3.1.7 Reversibility of 2-butyl-1,1,3,3-tetramethylguanidinium alkylcarbonates…………………………………………..... 127 3.3.1.8 Comparison of 2-butyl-1,1,3,3-tetramethylguanidinium alkylcarbonates…………………………………………..... 132 3.3.1.9 Miscibility studies of the 2-butyl-1,1,3,3 -tetramethylguanidinium alkylcarbonate ionic liquids…..... 133 3.3.1.10 2-butyl-1,1,3,3-tetramethylguanidinium bicarbonate…….. 135 3.3.1.11 Modification of the Structure of the Guanidine and its Affect on Physical and Chemical Properties …………....... 135 3.3.1.11.1 Alcohol Attached to Guanidine – 1 Component IL System……………………………………………… 136 3.3.1.11.2 Attaching Silicon groups to the Guanidine Core…... 136 3.3.1.11.3 Pentamethyl Guanidine…………………………….. 141 3.3.1.11.4 2-allyl-1,1,3,3-tetramethylguanidine……………….. 144 3.3.1.12 Applications of TMBG/TMBG MC IL system………….. 146 3.3.1.12.1 Reaction/Recycle of TMBG-methanol IL systems… 146 3.3.1.12.2 Base Catalyzed Reactions in TMBG………………. 148 3.3.1.12.3 Base Catalyzed Reactions in TMBG MC IL – Oxidation of benzyl alcohol………………………... 155 3.3.1.12.4 Summary of Reactions run in TMBG-methanol IL systems……………………………………………... 157 3.3.1.12.5 Separation of alkanes from tar sands/shale………… 157 3.3.1.12.6 Summary of other TMBG IL Applications………… 162 3.3.2 One Component Ionic Liquids..................................................... 162 3.3.2.1 Amine Precursor Molecules................................................. 162 vii 3.3.2.2 Synthesis and Characterization of One Component Ionic Liquids................................................................................. 163 3.3.2.3 Reversibility of One Component Ionic Liquids…………... 165 3.3.2.4 Miscibility Studies of the One Component